Sulphuric acid esters of alcohol ethers containing a carbocyclic group



Patented June 11,

- UNITED STATES PATENT OFFICE sULruUaIc ACID ESTEBS or ALCOHOL ETHERS GROUP CONTAINING A OARBOCYOLIC Adolf Steindorfl, Gerhard Balle and Paul Hcimke,

. Frankfort-on-the-Main, and Karl Horst, Hofheim in Taunus, Germany, assignors to *I. G. Farbenindnstrie Aktiengesellschaft, Frankfort- .on-the-Main, Germany No Drawing. Application May 4, 1937, Serial No. 140,706. In Germany December 12, 1935 Claims.

The present invention relatesv to sulphuric acid esters of alcohol ethers containing a carbocyclic group.

Thisapplicationis a continuation-in-part, of U. S. Patent No. 2,083,482. I

We have found that organic compounds having an acid character are obtainable byintroducing into the hydroxyl group of an aromatic or hydroaromatic hydroxy-compoundw'hich con tains as a substituent in the nucleus at least one aliphatic radical with more than three carbon atoms, an aliphatic radical whichfiontains an acid salt-forming group, and whose carbon chain is interrupted at least once by oxygen, nitrogen,

sulphur or the like a The new compounds correspond with the general formula: ROR1X wherein R means an aromatic or hydroaromatic radical containing as a substituent at least one aliphatic or aliphatic-aromatic radical with more than three carbon atoms and which may contain another substituent, R1 means an aliphatic radical the carbon chain of which is interrupted at least once by oxygen,'nitrogen, sulphur or the like and X' means an acid salt-forming group. In the form of their water-soluble salts the new bodies are for the greater part nearly colorless powders or viscous masses which are more or less easily soluble in water according to their v molecular weight and composition.

The free acids are in part crystalline bodies, in part oily liquids or viscous masses; some "of them are soluble in water as; for instance, the

, sulphonic acids, and glycclic ether carboxylic acids, others are insoluble in water. 1

The new compounds may be-made as follows: In order to introduce the aliphatic radicals in question R1-X into alkylated phenols orallgvlated hydroaromatic hydroxy compounds there may be'used the corresponding ready-made aliphatic bodies, that is to say an alkylated phenol or an alkylated hydroaroma'tic'hydroxy-compound is caused to react with, for instance, betachlor-diethylether-beta'-sulphonic acid; alternatively, a suitable aliphatic radical may be first' introduced into the aromatic or hydro-aromatichydroxy-compound by a single reaction or by several reactions and then the acid salt-forming group is introduced.

As parent material for the manufacture of the new compounds there may be used as alkylated aromatic hydroiry-compounds: para-n-butylpheno], amylcresol, di-iso-butylphenol, iso-heirylnaphthol, oleylphenol, iso-dodecylphenol, isooctylresorcinol and the like; as alkylatedhydroaromatic compounds. a

aromatic hydroxy-compounds, for instance; di-iso-butylcyclohexanol, iso-hexylcyclohexanol and the like. The hydroaromatic compounds may be made, for instance, by a catalytic nuclear hydrogenation of the aforesaid corresponding These bodies may be caused to react, as stated above, with bodies which contain a reactive halogen atom, an oxygen-, nitrogenor sulphuroridge and an acid salt-forming radical. As example ofsuch a body there has been mentioned the beta-chlordiethyl-ether-beta' sulphoni ti 2 cm e new compounds may also be made in stages, for instance, by causing one of the said parent materials to react with a halogen-hydrine or an alkylene oxide to form a product of the probable constitution:

- oaon dical, and introducing in known manner an acid salt-forming group into the product obtained,

for instance, by reaction with a halogen fatty acid, by a partial esteriflcation with a dibasic wherein R means an aliphatic hydrocarbon ra- I aliphatic carboxylic acid, by introduction. of ra-.

dicaland a: means 1, or a higher whole number.

By this sequence of reactions bodies are obtained in which the aliphatic radical carrying the acid group is interrupted at least once by oxygen.' In an analogous manner there may be obtained bodiesin which the said radical is inof the following probable constitution are 011- Y terrupted by nitrogen or sulphur. For instance,

' an alkyl phenol or an oxalky'lated phenol may be esteriiled with thiodiglycolic acid, or an alkylated phenol is caused to react with a halogen-albisulphonic acid. the corresponding sulpho-chloride made therefrom is reduced to the sulphinic acid and halogen fatty acid is caused to react therewith, whereby bodies of the probable constitution:

o.R.s0,R..oooH

alkyl are obtained.

' In the form of their water-soluble salts the new acid compounds possess a considerable capacity for reducing surface tension, so that they may be used with special advantage in the textile industry, for instance as wetting, emulsifying, dis-'- persing and cleansing agents as well as in the leather industryand in all cases where substances capable of reducing surface tension are required. Some of the said compounds may also be used in the pharmaceutical art.

The water-soluble salts of-the new sulphuric acid esters may be used as such or in combination with other products, for instance, with products having capillary-active properties such as soaps,

preparable by causing 2 mols of ethylene oxide to act upon 1 mol of tertiary octylphenol or by causing tertiary octylphenol-sodium to react with the equivalent quantity of diglycol-mono-chlorhydrine: C1.CH2.CHz.O.CH2.CH2.OH, are dissolved in 500 parts of diethyl ether and the solution is,

cooled to +5 C. parts of chlorosulpihonic acid are then causedto'run in. while wellstirring, care being taken that the temperature does not exceed +15 C. All of the 'chlorosulphonic acid having been introduced, the melt is further stirred for a short time and then poured on 300 parts of ice, the whole is well mixed and neutralized by means of a caustic soda solution of 40% strength, about 175 parts of the latter-being necessary.

As soon as the mixture shows a feebly alkaline reaction, the etheris distilled 01! under ordinary pressure, the water being distilled under reduced pressure. There remains a soap-like mass which solidifies .oncooling and which may be pulverized. The product is the sodium salt of the sulphuric acid ester of tertiary octyl-phenyl-diglycol ether. It is soluble in water, its solutions foam very strongly and are suitable for wetting textiles.

'(2) 394 parts of iso-dodecylphenyl-triglycol ether: C12H:5CsH4.O(CH 2.CI-I2.O):1H obtainable by condensing-phenol with the mixture of olefines containing about 12 C-atoms and formed by polymerization of propylene and reacting with 3 mols of ethylene oxide are dissolved in v500 parts of methylene chloride and the solution is cooled to +5 C. 140 parts of fuming sulphuric acid con-v taining 20 per cent. of sulphuric anhydride are then caused to run' in, care being taken that the temperature of the solution 'does not exceed +15 C. Thereupon, the mixture is further stirred for 2 hours at 10 C. 400 parts of finely ground ice are then added, while stirring, to the mixture and the whole is rendered neutral to litmus by addition of" a caustic soda solution, about parts of a caustic soda solution of 40 per cent. strength being necessary. After distillation of the solvent and about 80 parts of water, which pass over when removing the last portions of the solvent in vacuo, 1000 parts. of an aqueous paste (of about 50 per cent. strength) of the sodium salt of the acid sulphuric acid ester of the iso-dodecylphenyl-triglycol:

are obtained which still contains, beside water, some sodium sulphate. The paste dissolves in water to a clear, strongly foaming solution having a good power for washing white goods.

(3) $70 parts of a polyglycol ether, the poly- -glycol ether chains of which consist of about 5 ethenoxy groups and are bound to a mixture of alkyl phenols mainly consisting of iso-decyl-cresols and having the formula:

' acid, the mass has become rather viscous and isfurther stirred for about 4-6 hours, at a temperature of about 15 C. to 18 C. d50 parts of ground ice are then added and. the whole is neutralized by means of about parts of a caustic soda solution of 4 0 per cent. strength. The solution is mixed with a saturated sodium sulphate solution containing}. 1280 parts of sodium sulphate, and the mixture is dried in a drying apparatus, for instance on a'drying roll, orby atomizing.- A colorless powde'lj'is obtained which contains, be-

side 20% of the sodium salt of the acid sulphuric acid ester of the above defined alkyl cresyl-polyglycol ether, 80% of sodium sulphate. The powder may be used-as washing agent.

A very eifective washing agent is obtained,

when adding to the powder also sodium carbonate; an alkali salt of a phosphoric acid, a

bleaching agent, such as sodium perborate and a stabilizing agent for the latter, for instance, magnesium sulphate or magnesium silicate. v

(4) Phenol is condensed with an oleflne-mixture prepared by polymerization of propylene by 262 parts of this product are mixed with -2 parts of a caustic soda solution 'of 40 Be, and ethylene.

oxide is introduced, at about 160. C. (3., into the mixture until the increase ofweight corresponds to an absorption of 532 parts of ethylene f polyglycol ether obtained is soluble in water and has good properties of capillary action.

. 00 meansof phosphoric acid and containing chiefly .iso-dodecylene to form the iso-dodecyl-phenol.

- 80 parts of this polyglycoi ether are dissolved in 150 parts of diethyl ether and'they are transformed into the sulphuric acid ester of the doon ice. and the'solution of the sulphonate is neutralized by means of caustic soda solution and rendered feebly alkaline to phenol-phthalein. The ether is removed by heating and the solution of the sodium salt is evaporated to dryness. A viscous mass is obtained which is easily soluble 'in water and the solutions of which have a good foaming and wetting power.

There may also be used, instead of the isododecylphenol, other isomeric dodecylphenols, for instance such as are prepared by condensation of phenol and an'iso-dodecylene obtainable by dimerization of the iso-hexylene preparable by dehydrating the iso-hexyl alcohol formed, beside other alcohols, during the'reduction of carbon oxide; furthermore, there may be used, for instance, a dodecylphe'nol prepared by condensation of phenol with the mono-chlorination product of a middle oil from natural or synthetic hydrocarbon oils consisting, for the main part, of hydrocarbons containing 12 carbon atoms; there may be used also n-dodecylphenol preparable, for instance, by condensation of phenol with lauric acid to obtain the p-hydroxy-laurophenone and by re- V duction of this product to the p-dodecylphenol or the dodecyl-cyclohexanol.

(5) By polymerization of propylene in the presence of phosphoric acid there may be obtained a polymeric olefine containing about 9 carbon atoms. By condensation of such iso-nonylene fractions with phenol, in the presence of AlCla, BFJ, H2804 and the like, there is obtained a mixture of isomeric isononylphenols which may be transformed, by catalytic reduction with nickel catalysts. into a mixture of isomeric iso-nonyl-cyclohexanols.

, 400 parts of a polyglycol ether of these iso-' nonylcyclohexanols, the polyglycol ether radical of which is, in general composed of 3 propylene oxide molecules'having the formula:

CUHll-CIHM. E0 Hr-l? HJDTH CHa are dissolved in 600 parts of liquid sulphurous acid. 140 parts of chlorosulphonic acid are introduced into the solution, the reaction heat formed being paralyzed by the cold due to the evaporation of the sulphurous acid. The solution is then' neutralized by means of 300 parts of a caustic soda solution of 20 per cent. strength, whereby nearly all of the solvent is distilled ofl. The-residue is rendered feebly alkaline to phenolphthalein -may be condensed, by means of BF: and"beta-, naphthol to formthe iso-dodecyl-beta-naphthol. By treating this naphthol derivative with glycide,

-a polyglycerine ether of the iso-dpdecyl-betanaphthoi of the foilcwlna constitution is obtained:

682 parts of this pcly-glycerine ether are dissolved in 600 parts of carbon tetrachloride, and 100 parts of sulphuric monohydrate are caused to run, while well stirring, into the solution which has been cooled to +5", care being taken that the temperature does notexceed C. The mixture is further stirred at 15 C.- 6., for" about 1-3 hours, and it is then poured, while stirring, on about 400' parts of ice-water. The whole is then neutralized by means of a caustic soda solution of per cent. strength, about 100-110 parts being necessary. After distillation of the solvent and the water, the latter being best performed under reduced pressure, a viscous blackbrown meltis obtained, the sodium salt of the acid sulphuric acid ester of the iso-dodecylnaphthol-poly-glycerine ether. v (7) When using, as indicatedin Example 6, a fraction of the high-boiling products obtained by the synthetic preparation of methanol or isobutyl-alcohol and containing, for the main part,

isohexyl and isoheptyl alcohol, and treating it in the same manner, a mixture is obtained containing, on an average, oleflnes with 13 carbon atoms. The olefine mixture obtained is condensed in known manner, by means of crude cresol to form a crude C-alkyl-cresol and catalytically hydrogenated' to a mixture of C-alkyl-methyl-cybloide to act upon the productof hydrogenation, a polyglycol ether of the following constitution is obtained: v i

1 600 parts of this ether are caused to run slowly r hexanols, By causing 2 mols of 1,2-butylene oxinto 186 parts offuming sulphuric acid containing 20% of sulphuric anhydride the temperature of the sulphonatlon mass being maintained at about 15 C.-about 18 C.. The mass is further stirred, for about 4 hours, at 18 and 910 parts oi. ice are added thereto, the mass is then neutralized with about 300 parts of a caustic soda solution of 40 per cent. strength. The resultant paste consists to 35% of the SOdllll'l'i salt of the alkyl methyl-cyclohexyl-polybutanol ether; it contains,

beside water, sodium sulphate. It-d'issolves in water to clear solutions which possess a good cleansing power.

(8) By condensation of stearic acid chloride with phenol according to the Friedel-Craft reaction. the p-stearo'yl-phenol is obtained beside the o-stearoylphenol. By causing 15 mols of ethylene oxide to act upon the above mentioned ketone, a polyglycol ether of the following formula is ob.- tained: Cr'iHas.CO.CcH4.O(CH2.CI-Iz.O)15H.

1000 parts oi. this ether are dissolved in'1500 parts of diethyl ether and a mixture of 174 parts of chlorosulphonic acid and 200 parts of diethyl' tion of the diethyl ether, the water is distilled off under slightly reduced pressure. Therefemains the potassium salt in the form of a wax-like near- 1y colorless mass.

450 parts of the polyglycol ether of the formula: CmHza.CcHa(CI-Ia)0'(CHz.CHz.O) 4H obtainable'by condensation of commercial cresol with the mono-chlorination product of a middle oil formed during the hydrogenation of coal and containing, for the main part, hydrocarbons with 12 carbon atoms and by treatment of the alkylcresol formed with 4 mols of ethylene oxide, are sulphonated, at 10 C.-15 C., by means of 180 parts of fuming sulphuric acid containing 20% of sulphuric anhydride. The whole is further stirred for 6-8 hours, 450 parts of ice are added thereto and the mass is neutralized with 300* parts of an ammonia solution of 1'7 percent. strength, the temperature not exceeding +20 C. An aqueous paste is obtained which contains 40% of the ammonium salt of the acid sulphuric acid. ester of the iso-dodecyl-cresyl-polyglyco1 ether. 1 (10) 574 parts of the polyglycol ether:

GEE-- preparable by condensation of hydroxy-diphenyl with tertiary butyl-alcohol and subsequent treatment of the tertiary butyl-hydroxy-diphenyl with 6 mols of propylene oxide, are sulphonated, at 5 C.-12 (3., by means of 1'74 parts of chlorosulphonic acid; the mixture is subsequently stirred for 4 hours, 600 parts of ice are then added thereto and the whole is neutralizedby means of 270 parts of a caustic soda solution of 40 per cent. strength. After distillation of the water in vacuo, a viscous soft-resin-like product is obtained, the

sodium salt of the acid sulphuric acid ester of the tertiary butyl-diphenyl-polypropylene-glycol ether. I

(11) Into the di-isobutyl-phenol of the following constitution:

there may be introduced polyglycol ether chains of different length, by treating thephenol, at about 140 C.-160 C., with ethylene oxide in the presence of a small amount of caustic potash; products of the following general constitution are obtained:

OICHi-CHLOLH- oil! wherein n may be every whole number greater than 1, the'upper limit for n being, for the present invention, about 100. All these polyglycol others may be transformed, by one of the methods indicated in the preceding examples, into the acid sulphuric acid esters or their sodium salts.

(12) 206 parts of para-tertiary octylphenol (obtainable by condensing phenol with di-isobutylene) are melted and 2 parts of a caustic soda solution of 40 per cent. strength are added thereto. Ethylene oxide is introduced, while stirring, at a temperature of 120 C.-150 C. until 6-mols of ethylene oxide per one mol of paratertiary octylphenol have been absorbed. An oil aaoases is obtained which is soluble in water except for a slight turbidity and which is an excellent cleansing agent for woolen fabrics. 470 parts oi. this tertiary-octylphenyl-polygl'ycol ether having a polyglycol'ether chain consisting of 6 mols of gly- ('13: CH: cut-ccHr-+-Oo omom0)m OH; on,

are dissolved in 600 parts of ether and 120 parts of chlorosulphonic acid are added to this solution at about C. to about 20 C. while well stirring, The dissolved hydrogen chloride is eliminated by blowing in dry air; thereupon, the solution is diluted with ice water and rendered feebly alkaline to phenolphthalein by means of caustic soda solution at a temperature not exceeding +30 C. r The sodium salt of the acid sulphuric acid ester of an iso-octylphenyl-polyg-lycol ether with an average content of 6 glycol radicals dissolves in water to a clear solution. The product constitutes a very good wetting agent for wool and cotton.

Instead of para-iso-octylphenol there may be used the mixture of alkylphenols obtained by condensing phenol with the commercial polymerization product of iso-butylene containing beside di-p iso-butylene tri-iso-butylene and other oleflnes.

(13) 206 parts of tertiary octylphenol, prepared by condensing di-iso-butylene with phenol in the presence of boron-fluoride, are mixed with 0.7 part of powdered caustic soda and heated to 120 C.-130 C. under reduced pressure until the product is anhydrous. Propylene oxide is then introduced at a temperature between 160 C. and 180 C. until 580 parts of propylene oxide have been absorbed. A water-insoluble oil is obtained.

This oil may be made soluble in water by convertingit into an acid sulphuric acid ester, for instance, as follows:

786 parts of the tertiary-octylphenyl-polyhydroxypropyl ether CHI are dissolved in 1000 parts of ether and 120 parts of chlorosulphonic acid are slowly introduced into the solution, while well stirring, at a temperature of about 15 C. to about C. The hydrochloric acid gas formed is then removed by means of a weak current of air. diluted with ice water, the whole is made feebly alkaline to phenolphthalein by means of caustic The ethereal solution is soda solution, the ether is first evaporated and p then the aqueous solution is evaporated to dryness. There is obtained the sodium salt of the tertiary.-octylphenyl-polyhydroxyl propyl ether sulphonate in the form of a vitreous water-soluble mass.

(14) 262 parts of tri-iso-butylphenoi GoHr- 04B. are treated with 220 parts of ethylene oxide according to the described methods. tained a polyglycol ether containing in the polyglycol radical about 5 etheneoxy groups. By causing 482 parts of this oily product which may be emulsified with water to react at about 10 C. to

There is obtaining 500 parts of the sodium salt of the sulphurio acid ester of the iso-dodecylphenyl-tri-- glycol ether. is adjusted to the desired concentration. The product has, when diluted in a about 15 Qwith 120 parts of chlorosulphonic acid in a diethylether solution, there is obtained the corresponding sulphuric acid ester. The sodium salt of this ester is a product whichis soluble in water to a clear solution. Thesesolutions foam very strongly and are suitable for washing woolen, cotton and rayon fabrics.

(15) 130 parts of vchlorosulphonic acid are gradually introduced, at C.-10 C., intoa well stirred mixture of 392 parts of iso-dodecylpbenyltri-glycol ether as described in Example 2 and 600 parts of ethylene dichloride and the whole is stirred, for further 3-5 hours, at about 30- C. The reaction mixture is neutralized, while coollng, with dilute caustic soda solution, the solvent is blown oil and the clear aqueous solution consuitable manner, good washing, dispersing and, also in combination with other washing agents, a good foaming power.

(16) At 10 C.-30 C., 294 parts of iso-octylphenyl-diglycol ether obtainable by condensing phenol with alpha-ethylh'exyl alcohol in the presence of ZnCla and reacting with 2 mols of ethylene oxide and having the formula:

are caused to run into 200 parts of sulphuric" acid of 100 per cent. strength and the whole is stirred, at about 30 C., until a test portion of the product is, after neutralizing, soluble in water, which occurs in most cases after 3-4 hours. The sulphonation mixture is poured on ice and water and neutralized with caustic soda solution. After evaporation, a viscous salt mass is obtained which contains 396 parts or the sodium salt of the sulphuric acid ester o! the above diglycoi ether. (17) 206 parts of tertiary-octylphenol (molecularflweight: 206) of the formula:

CHI

cm OHi-JJ-CHg-Ai" on I are dissolved in 500parts of an alcoholic caustic soda solution containing 40 parts of NaOI-I. Into the solution boiling on the water-bath in a reflux apparatus, there is introduced, while stirring, an alcoholic solution of 230 parts of the sodium saltof the acid sulphuric acid ester of the beta-chloro-beta'hydroxy-diethyl ether:

C1.CH2.CHa-O.CHaCHmOBOaNa After a short boiling, the quantityof sodium chloride the separation at which begins immediately does no longer increase. The whole is allowed to cool, the product is filtered with suction from the sodium chloride and the solvent is distilledoii, the latter operation'beingflnally performed under reduced pressure. The sodium salt 01 the sulphuric acid ester of the tertiary-' octylphenyl -diglycol ether is obtained; The product is soluble in "water. v It.s solutions are appropriate for being used as wetting agents. 1 (18) 244 parts or p-benzylphenoxy-ethyl-hy- 'drosulphide l a oestoinsn' mo able w reaction r p-benlylphenol with 1 arouses molor ethylene sulphide, are caused to react, in an alcoholic caustic potash solution, with ethylone chlorhydrlne; thereby the hydroxy-ethyl sulphide oi the above compound is formed:

1 O.CH!.CHi-S.CHl-CHI.OH

288 parts of benzylphenoxy-ethyl-hydroxyethyi sulphide are dissolved in 300 parts-of diethyl ether. At about 15 C. to about 20 C., a solution of 145 parts of chlorosulphonic acid in 200 parts of diethyl ether is caused to run in. The sulphanation complete, 350-parts of ice are added to the mass and the whole is neutralized by introduction of 30 parts of ammonia. The solvent is then distilled off. A thick paste is obtained containing about 50 per cent. of the ammonium salt of the acid sulphuric acid ester of the abovementioned sulphide. The paste dissolves in water to a clear solution.

(19) '74 parts of glycide are caused to act, at 150 0., upon 235 parts of iso-hexyl-o-cresoxyethylamine:

300 parts or this amine are dissolved in 600 parts of methylene chloride, 100 parts or sulphuric acid or 95 per cent. strength are added thereto and, thereupon, there are introduced i203 parts of chlorosulphonic acid. After a short stirring at 10 C.-l 6.. the mass is caused to run into Gilli parts of a caustic soda solution of 2i per cent. strength which has been cooled to +5 (Ct, visorous stirring being necessary. The methylene chloride and the water are distilled an and the dry residue is extracted by means of hot alcohol .and' filtered from the sodium sulphate. The

alcohol having been distilled on, there remains the sodium salt oi the acid sulphuric acid ester formed in the form of a clear viscous mass. it

dissolves in water to a clear solution and its solutions have a good foaming power.

We claim:

1. The compounds of the general formula:

R.O.Ri.O.SOaH wherein R represents a member of the group consisting of aromatic and hydroaromatic radicals being substituted at least once by a member or the group consisting of aliphatic cycloallphatic and aliphatic-aromatic radicals with more than 3 carbon atoms, R1 represents a carbon chain which-is interupted at least once by a member or the group consisting of oxygen, sulphur and nitrogen, which in the form of their water-soluble salts possess capillary activity.

2. The compounds of the formula:

ammonnsosom Eiii cyclic radical being substituted at least once by an aliphatic hydrocarbon radical with more than 3 carbon atoms, R: stands Koran aliphatic hydrocarbon radical with at least 2 carbon atoms. R2 represents an aliphatic hydrocarbon radical and n means a whole number, which in the form of their water-soluble salts possess capillary activity.

3. The product of the formula:

wherein R stands for a mixture of radicals of mineral oil hydrocarbons containing about 12 carbon atoms, the water-soluble salts of which are I of capillary activity.

asosees wherein R represents a six membered 'cairbo *s. wa sold sulphuric acid ester Gripe for-.- mula:

, on. ch. 7 mo- -ca,- owmomoisscia' the water-soluble salts of which are of capillary activity.

5. The product of the formwla:

Es GEBEMWE- 0% m igsosm whei'eln R stands for a mixture of alkyl radicals consisting substantially of tridecyl, the watersoluble salts of which are of capillary activity.

ADOLF STEINDORFF.

GERHARD BALLE.

- PAUL HEIMKE. KARL HORST. 

